Dodecahydrocarbazole amides



United States Patent 3,014,920 DODECAHYDROCARBAZOLE AMIDES HansDressler, Pitcairn, and Melvin E. Baum, Pittsburgh,

Pa., assignors to Koppers Company, Inc., a corpora- "ice In the formulashown hereabove, R is a substituent chosen from the following group:alkyl having preferably up to 18 carbon atoms, hydrogen, amino,carboxyalkyl, carboxyaryl, carboxyalkenyl, carbalkoxyalkyl,hydroxyalkyl,

tion of Delaware 5 aminoalkyl, haloalkyl, cyanoalkyl, arallryl andalkaryl. No Drawing. Filed June 1 1959 S No. 20 617 The compounds of theinvention derive their plasticiz- 3 Claims (CL 2 0 315 mg andantioxidant properties from the presence in their structure of thedodecahydrocarbazole nucleus and the This invention relates to certainacylated derivatives acyl group. Their specific physical properties varyto of heterocyclic amines. In one specific aspect, it relates 10 someextent with the group or radical represented by to noveldodecahydrocarbazole amides. R in the above formula; thus, they rangefrom high-boil- Dodecahydrocarbazole, ahydrogenation product of caringliquids to high-melting crystalline solids depending bazole, is apromising chemical intermediate because of upon the particular R groupwhich they contain. When its solvent solubility, relatively low meltingpoint and the they are added to polymeric materials such as polyamidesbasicity of its amino nitrogen. Known derivatives of and polystyrene insmall amounts, e.g. from 0.05-5 perthis interesting compound arerelatively few, possibly cent by weight they serve as plasticizers witha mild antibecause of the expense heretofore involved in itspreparaoxidant effect. tion. Recent refinements in the hydrogenation ofcar- The novel compounds are prepared by reacting dodecbazole (whichoccurs in coal tar to the extent of 23 ahydrocarbazole with at least astoichiometric quantity of percent in the anthracene fraction thereof)have made doan acylating agent in the presence of a suitable solventdecahydrocarbazole readily available. over a wide variety oftemperatures and pressures. The Quite surprisingly, we have found a newclass of dodecmole ratio of reactants used is not critical and thus canahydrocarbazole amides which are remarkably effective be varied widelyasdesired. as plasticizers and antioxidants for polymeric materials. Thechoice of acylating agent varies with the particular It is, therefore,an object of the present invention to compound desired. Generally, theuseful acylating agents provide a new class of dodecahydrocarbazolederivatives comprise esters, acids, acid anhydrides, or acid halideswhich are useful as plasticizers for a wide variety of resins having thedesired substituent thereon. For example, and which, in addition, tendto inhibit oxidation of resins to make the compounds wherein R iscarboxyalkyl, carcontaining such derivatives. boxyaryl orcarboxyalkenyl, an acid anhydride is con- In accordance with theinvention, we have discovered veniently used. An ester, e.g. methylformate, is used chemical compounds of the formula: to prepare compoundswherein R is H. Compounds wherein R is NH are readily prepared using asan acylat- S 0 ing agent urea or an alkali metal cyanate. Acid chloridesN it B are elfective acylating agents for the preparation of com- Tpounds wherein R is alkyl. A few specific useful acylating agents andthe resulting products are shown below in Table I.

TABLE I Acylating Agent Name of Product Structure of Product S i!Propionyl chloride 9-Propionyldodeca- NOCrHr hydrocarbazole.

0 Stearoyl chloride Q-Stearoyldodeea- N-ii-QvH hydrocarbazole.

fi-propiolactone oride Monochloroacetyl chloride.

9-(3-hydroxypro- N-C-CflHAOH pionyl) dodecahydrocarbazole.

3 TABLE I-Continued Suitable solvents for the reaction include esters,aromatic hydrocarbons and ethers. If an ester is used as the acylatingagent, it may also serve as a solvent for the reaction if sufiicientexcess thereof is present. The reaction temperature is not critical andis limited only by the boiling point of the particular solvent used. Itis preferable to use a temperature in the range of -200 C. The reactionworks well at atmospheric pressure although higher or lower pressurescan be used, if desired. The reaction time varie between a few minutesto several hours, depending upon the nature of acylating agent chosen.

Our invention is further illustrated by the following examples.

Example I 9-DODECOYLDODECAHYDROCARBAZOLE A mixture of 251 grams (1.4moles) of dodecahydrocarbazole, 1600 ml. of xylene and 154 grams (0.7mole) of lauroyl chloride was stirred and refluxed for 4 hours. Aftercooling to 25 C., the mixture was filtered. The solvent was washed with300 ml. of xylene and dried to give 99.2 grams (69 percent yield) ofdodecahydrocarbazole hydrochloride. The filtrate was concentrated,cooled to C. and filtered to give an additional 55.5 grams of crudedodecahydrocarbazole hydrochloride. The filtrate was stripped of xyleneand the residue was distilled through a 4 inch Vigreux column to give220 grams of a pale yellow oil (B.P. 247-252C. at 3 mm. of Hg). Theproduct was identified as 99 percent pure 9-dodecoyldodecahydrocarbazole by nitrogen analysis. The yield was 87percent of theory. Calculated for C H NO: N, 3.88; Found: N, 3.84.

Example II 9-CARBAMYL-DODECAHYDROCARBAZOLE A molten mixture of 18 grams(0.1 mole) of dodecahydrocarbazole and 12 grams (0.2 mole) of urea wasstirred at 160 C. for 5 hours. The mix was then poured into 100 grams ofcrushed ice and filtered. The solid was washed with water to removeexcess urea. The insolubles were ground under ether and filtered to give19.6 grams (88 percent yield) of the crude9-carbamyl-dodecahydrocarbazole. After 3 recrystallizations from aqueousethyl alcohol, a relatively pure product, M.P. 180182 C., was obtained.

Example III 9-CARBAMYL-DODECAHYDROCARBAZOLE The hydrochloride ofdodecahydrocarbazole was formed by adding 25 ml. of 2 N hydrochloricacid (0.05

mole) to 9 grams (0.05 mole) of dodecahydrocarbazole. The reactionmixture was cooled to 25 C. and 4.1 grams (0.05 mole) of potassiumcyanate was added thereto. The mixture was allowed to stand for twohours with occasional stirring. A crystalline solid was filtered otf,washed with 50 ml. of water and 25 ml. of ether and then dried to give8.1 grams (74 percent yield) of 9-carbamyl-dodecahydrocarbazole. Afterrecrystallization from benzene, colorless crystals melting at 167170 C.were obtained and were shown to be 97 percent pure product by nitrogenanalysis. Calculated for C H N O: N, 12.6; Found: N, 12.2.

Example IV 9-FORMYLDODECAHYDROCARBAZOLE A mixture of 36 grams (0.2 mole)of dodecahydrocarbazole and 15 grams (0.25 mole) of methyl formate wasrefluxed on a steam bath for one hour. The methanol formed during thereaction and excess methyl formate were distilled off. The residue wasfractionally distilled to give 21.8 grams (53 percent yield) of9-formyldodecahydrocarbazole as a colorless liquid boiling at 157159 C.at 4 mm. of Hg. Calculated for C H NO: N, 6.77; Found: N, 6.51.

Example V 9- 3-CARBOXYPROPIONYL) DODE CAHYDRO CARBAZOLE A solution of 18grams (0.1 mole) of dodecahydrocarbazole, 10 grams (0.1 mole) ofsuccinic anhydride and 25 ml. of ethyl acetate was refluxed for one hourand then held at 5 C. for 16 hours. The product was filtered to give 19grams (68 percent yield) of colorless crystals melting at 109114 C.After recrystallization from ethyl acetate, crystals melting at 111-115"C. were obtained. The product was found to be 97 percent pure9-(3-carboxypropionyl)dodecahydrocarbazole by acid-base titra tion.Calculated for C H NO Neutral equivalent, 279; Found: Neutralequivalent, 271.

Example VI Example VII 9- (O-CARBOXYBENZOYL) DODECAHYDRO CARBAZOLE Amixture of 15 grams (0.1 mole) of phthalic anhydride and 18 grams (0.1mole) of dodecahydrocarbazole was dissolved in 50 ml. of ethyl acetateand heated on a steam bath for 2 hours. After cooling to 5 C., themixture was filtered to give 24.2 grams (74 percent yield) of acolorless solid melting at 182-l87 C. After recrystallization from 50percent ethyl alcohol, crystals melting at 207209 C. were obtained. Theproduct was found to be 97 percent pure9-(O-carboxybenzoyl)dodecahydrocarbazole by acid-base titration.Calculated for C H NO Neutral equivalent, 327; Found: Neutralequivalent, 337.

Example VIII 9- w-CARBOXYACRYLYL) DODECAHYDROCARBAZOLE A solution of 18grams (0.1 mole) of dodecahydrocarbazole and 10 grams (0.1 mole) ofmaleic anhydride in 25 ml. of ethyl acetate was refluxed for one hour,then cooled to 5 C. and held for 16 hours. After filtering, 14 grams ofa colorless solid (50 percent yield) melting at 122126 C. was obtained.After recrystallization from ethyl acetate the product melted at 124129C. By acid-base titration it was shown to be 97 percent pure9-(w-carboxyacrylyl)dodecahydrocarbazole having the formula shown below.

Calculated for C H NO Neutral equivalent, 277; Found: Neutralequivalent, 270.

We have thus provided a new generic class of dodecahydrocarbazoleamides. In addition to their uses as plasticizers and antioxidants,these interesting compounds show promise as lubricants, thickeningagents and textile adjuvants. Thus, the compounds of the invention,particularly those wherein R is carboxyalkyl, carboxyaryl,carboxyalkenyl, carbalkoxyalkyl and hydroxyalkyl, can be added totextile-treating baths in amounts ranging between 0.25 and 2 percent toimpart antistatic properties to the textiles being treated. Certain ofthe compounds, e.g. 9-carbamyl-dodecyahydrocarbazole, are excellentlubricants and thickening agents. For example, they can be admixed withstyrene-maleic anhydride copolymers in an amount ranging about e.g. 1-5percent to provide 6 a useful thickener for paints, varnishes and thelike. The 9-formyl dodecahydrocarbazole is an excellent high-boilingsolvent, especially for nitro compounds.

We claim: 1. A compound of the formula:

wherein R is a member selected from the group consisting of carboxylower alkyl, carboxy lower alkenyl, carbalkoxy lower alkyl, hydroxylower alkyl, cyano lower alkyl and amino lower alkyl.

2. 9-carbamyl-dodecahydrocarbazole.

3. 9-(3-carboxypropionyl) dodecahydrocarbazole.

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1. A COMPOUND OF THE FORMULA: